Metallic salt of reaction product of phosphorus sulfide and alkylated cycloaliphatic alcohol



UNITED STATES PATENT OFFICE METALLIC SALT OF REACTION PRODUCT OF PHOSPHORUS SULFIDE AND ALKYLATED CYCLOALIPHATIC ALCOHOL Peter A. Assefl", Cleveland, Ohio, assignor to The Lubrizol Corporation, Wickliife, Ohio, a corporation of Ohio No Drawing. Application May 14, 1947, Serial No. 748,111

9 Claims. (Cl. 260-429) i. This invention relates as indicated to metal salts and their mode of preparation, and which is a continuation, in part and as to common sub- Ject matter, of my co-pending application Serial No. 416,604 now abandoned, which in turn was a continuation, in part and as to common subject matter, of my co-pending application Serial No. 404,361, filed July 28, 1941, now Patent No. 2,261,- 047.

phorus which also contain sulphur.

A preferred class of compounds are those which may be produced by:

2 (a) Reacting together an alkylated cycloaliphatic alcohol, a reagent containing phosphorus and sulphur, and a basic polyvalent metal compound, such as for example, polyvalent metal oxide, polyvalent, metal carbonate or basic polyvalent carbonate; or

Reacting an alkylated cycloaliphatic alcohol with a reagent containing phosphorus and sulphur to form an acid ester either directly It is a principal object of my invention to pro- 10 or by subsequent hydrolysis of the reaction vide as a novel composition of matter certain product, and finally forming the polyvalent metallic salts which while useful as addition metal salt of such acid ester, either directly agents in lubricating compositions as claimed in by reaction of the acid ester with a basic my above-identified parent application, neverthepolyvalent metal compound, or indirectly by less, have a wider field of utility. The mode of first forming an alkali metal salt and then preparation of these new compositions of matter reacting the latter by double decomposition is also believed to be novel and produces materials with a water soluble polyvalent metal salt. heretofore not available.

A preferred class of the cyclic alcohols are the mother f of the mventlon Wm appear as cycloaliphatic alcohols and particularly those zg pt on fig t d which contain the cyclohexyl nucleus, eitherin a o e q en of the foregoing an non-condensed form such as may be derived by related ends, said invention then comprises the hydrogenation of the phenyl group or in com features hereinafter fully described and particudensed form such as may be derived by hydm larly Pointed m the clams the following genation of condensed aryl radicles such as naphscription setting forth in detail certain illustrathyl anthracyl and phenanthryl tive embodiments of the invention, these being ItiS also desirable that the cyblic alcohol have indicative, however, of but a few of the various one or more aliphatic substituents Such asfor ways in which the principle of the invention may example alkyl groups, a1koxy groups, and acyl be employed groups. A preferred class of alkyl substituents Broadbf Stated h invention may be defined are those which contain less than six carbon as compnsmg' as new compositions of matter atoms and particularly those which contain less those compounds each of which may be defined than four carbon atoms as a stable, oil-soluble compound which contains: For most purposes it'is desirable to select the (a) An organic radicle derived from an alkylated alcoPol fmm the class m which the hydr 0x371 p cycloanphatic alcohol; is directly attached to a carbon atom which is (b) A polyvalent metal; part of a cycloaliphatic ring structure, as for ex- (0 The element phosphorus; and ample 1n the case of cyclohexanol and substituted (d) The element sulphun cyclohexanols. However, cyclic alcohols of the naphthenyl type are also useful for. the purpose As indicated above, my invention is also conw of forming the compounds of this invention. cerned with the mode of manufacture ,of these The bridged ring" type of cycloaliphati 1- novel compounds. cohols is also among those which are preferred,

Certain of these compounds may be considered as for example those which may be considered as as the polyvalent metal salts of the acid esters derivatives of pinene, limonene, camphene, etc. formed by cyclic alcohols with those acids of phos- Another group of cycloaliphatic alcohols which are commercially available and useful for this purpose are those which may be considered as derivatives of the terpenes, menthenes and menas a? example, the terpineols, mez'ithol, ctc. From the foregoing it will be seen that these cycloaliphatic alcohols which contain:

(a) At least one cyclohexyl nucleus, and

it) At least one alkyl radicle, and.

(c) The hydroxy group directly attached to a W cioaliphatic ring structure are among the most desirable.

Among the types of alcohols which have these desirable characteristics are:

Alkylated cyclohexanols (hexahydro-alkyl phehols) Alkylated cyclohexyl cyclohexanols (dodecahy-= dro-alkyl-phenybphenols) Decahydro-aliryl-naphthols Sterols A specifically preferred group of alcohols are the alkylated cyclohexanols in which substantially all of the alkyl groups have less than six carbon atoms. Specific examples of this group are:

Mono-methyl cyclohexanols Poly-methyl cyclohexanols, e. g.- Dimethyl cyclohexanols Trimethyl cyclohexanols Monoand poly-ethyl cyclohexanols Monoand poly-propyl cyclohexanols, e. g.-

n-Propyl cyclohexanols Iso-propyl cyclohexanols Monoand poly-butyl cyclohexanols, e. g.-

n-Butyl cyclohexanols Sec-butyl cyclohexanols Tert.-butyl cyclohexanols Monoand oly-amyl cyclohexanols, e. g.-

n-Amyl cyclohexanols Sec-amyl cyclohexanois Tert.-amyl cyclohexanols Iso-amyl cyclohexanols Phosphorus and sulphur are derived in accordance with this invention from phosphorus pentasulphide.

In the foregoing broad statement of this invention the addition agent has been defined in terms of its mode of preparation and desirably and necessarily so on account of the difiiculty in a more precise identification of the molecule characterizing the product. As a matter of fact, the product contemplated is probably a mixture of different constituents and it is for this reason that the same is best defined, as above indicated, in terms of its mode of preparation.

Referring more specifically to the metallic salts prepared from phosphorus pentasulphide, these products may be prepared as indicated by reacting phosphorus pentasulphide with a cycloaliphatic alcohol in the preparation of an intermediate acidic reaction product and the polyvalent metal salt then prepared of such acidic reaction product.

Alternatively, and as likewise indicated above, the final product may be prepared in a single step or in concurrent steps by reacting together phosphorus pentasulphide, the alcohol, and polyvalent metal oxide. In this case, it is' probable that the reaction which forms the intermediate acidic reaction product, and the reaction of such acidic reaction product with polyvalent metal oxide to form the final salt, take place simultaneously.

The following is an inclusive list of cycloaliphatic alcohols which may be used in carrying out this invention:

Additional examples of cycloaliphatic alcohols which are useful for this purpose are:

Poly-alkylated cyclohexanols; e. g.-

Dimethyl cyclohexanol Diethyl cyclohexanol Dipropyl cyclohexanol Dibutyl cyclohexanol Diamyl cyclohexanol Trimethyl cyclohexanol Tetra-methyl cyclohexanol Triethyl cyclohexanol Tetraethyl cyclohexanol Tripropyl cyclohexanol Tetrapropyl cyclohexanol Cyclo-alkyl substituted aliphatic alcohols, e. 9,-

Cyclohexyl methanol (hexahydro benzyl alcohol) Cyclohexyl ethanol Cyclohexyl propanol Naphthenyl alcohols, i. e. alcohols produced by reduction of naphthenic acids Alkylated:

Hydrogenated naphthols, e. g.- Ac-tetrahydro-a-naphthol Ac-tetrahydro-p-naphthol Decahydro-a-naphthol Decahydro-p-naphthol Alkylated: hydrogenated anthranoi Allwlated: hydrogenated anthrol Alkylated:

Poly-hydric cycloaliphatic alcohols, e. g.-

Hydrogenated poly-hydroxy benzenes,

such as: 1

Hexahydro-catechol Hexahydro-resorcinol Hexahydro-hydroquinonc The cycloaliphatlc alcohols which may be used in this way include those which have substituent groups in addition to hydrocarbon substituents. The presence of such additional substituent groups is sometimes advantageous for particular purposes. Examples of such additional substituents are:

Organic substituents, e. g.-

n-oand R-OR' o o R-iiand a-g-a o o o n-oand R-0-ti-R'- and n- -o-ivwhereRis:

(a) Alkyl, such as- Methyl Amyl Ethyl. Lauryl Propyl Cetyl Butyl (b) Cycloalkyl, such as- Cyclohexyl Naphthenyl Cycloheptyl (c) Aryl, such as- Phenyl Tolyl Naphthyl Xylyl Xenyl and R is a divalent hydrocarbon radicle, e. g.--

(CH2)n-Sl10h as- Methylene Ethylene Propylene phenylene, -CeHe- Inorganic substituents, e. g.-

Cyanide (nitrile) The halogens Fluorine Chlorine Bromine Iodine Radicles derived from inorganic oxy acids,

such as- Sulphate Sulphite Sulphonic acid Sulphinic acid Sulphenic acid Nitrate Nitrite Nitro Nitroso Phosphate Phosphite Cyanate and iso-cyanate Radicles derived from inorganic thio-acids,

such as- Thiosulphate Thiophosphate Thiophosphite Thiocyanate and iso-thiocyanate sulphide, polysulphide, and hydrosulphide Additional examples of substituent groups are the groups obtained by substituting sulphur for one or more of the oxygen atoms in the substituents listed under organic substituents.

It is not necessary that the cycloaliphatic alcohol used for this purpose be a pure compound. It may consist of a mixture of cycloaliphatic alcohols and such mixtures are often particularly advantageous. An example of such material is the mixture of alcohols resulting from the hydrogenation of commercial Cresol. The methyl cyclohexanol referred to hereafter is the product thus obtained. A mixture of alkylated cyclohexanols consisting principally of ethyl and pro- Dyl cyclohexanols has also been found particularly suitable for this purpose.

The cycloaliphatic alcohols which contain the cyclohexane nucleus, for example the alkylated cyclohexanols, are particularly useful cycloaliphatic alcohols for my purpose because they are commercially available and producea product which has advantageous properties.

Of the cycloaliphatic alcohols in general those are preferred which have a total of less than t n carbon atoms. The alkylated cycloaliphatic alcohols are particularly suitable. In this case, it

' alkylated decahydro-naphthols and the alkylated dodecahydro-phenyl-phenols (cyclohexyl-cyclohexanols).

Those cycloaliphatic alcohols which contain an aromatic substituent may also be used. Examples of these are the alkyl-substituted: phenylcyclohexanols. benzyl cyclohexanols, tolyl-cyclohexanols, and benzoyl cyclohexanols.

While for most purposes I prefer to use those cycloaliphatic alcohols in which the hydroxyl group is directly attached to a carbon atom which is part of a cycloaliphatic nucleus, it is sometimes desirable to use cycloaliphatic alcohols which have thehydroxyl. group attached to a carbon atom which is part of a chain structure. Examples oi the latter are the alkylated naphthenyl alcohols and e-terpineol.

As will be pointed out more specifically hereinafter, of the polyvalent metals which are suitable for use in accordance with this invention, zinc has been found to be of particular value. However, it will be understood that polyvalent metals other than zinc, are likewise of utility. Among such metals are cadmium, magnesium, calcium, barium, strontium, mercury, copper, aluminum, lead, tin, chromium, manganese, iron, cobalt and nickel. The oxides, carbonates, basic carbonates, and hydroxides of the foregoing metals are the most convenient basic materials with which to produce the salts contemplated. Procedures involving double decomposition with the sodium salt of the acidic reaction "product of P235 with the alcohol may be substituted, however, for the direct neutralization reactions above contemplated,

Since a 's'pecific example of the new materials of the present invention which has been found of especial utilityis the zinc salt of the. acidic reaction product obtained by reacting phosphorus pentasulphide with methyl cyclohexanol, the details of the manufacture of such material will begiven as illustrative of the mode of manufacture of the smilar materials comprised within the broad statement of the invention.

This process may be divided into two parts, i. e.

(a) The preparation of the acid ester, and (b) The preparation of the metallic salt of such acid ester.

(0.) PREPARATION OF THE ACID-ESTER Five moles of methyl cyclohexanol and one mole of P285 were mixed with an amount of benzene equal in volume to the amount of cyclohexanol and placed in a flask equipped with a reflux condenser, a thermometer and a mechanical stirrer. The flask was placed in a water bath at approximately 100 F. and refluxed for four hours. The batch was then cooled to about 60 C. and washed once with an equal volume of water at 60 C. The benzene was removed from the wash material by distilfation at atmospheric pressure. A typical batch of the preparation of the acid estcr in the mode above defined was as follows:

Wt. of methyl cyclohexanol grams 500 Moles of methyl cyclohexanol 4.39

It is believed that the reaction between phosphorus pentasulphide and the alcohol produces a mixture of compounds of the type represented by acid thiophosphate esters. For example:

where The methyl cyclohexanol and zinc oxide are placed in a container and heated to 180 1". Then the phosphorus pentasulphide is added in finely divided form so that it will pass a 40 mesh screen.

R is the cyclo-aliphatlc radicle derived from the alcohol R is hydrogen or R The final product, if this assumption is correct, would then consist of the salts derived from the acid ester by replacingthe replaceable hydrogen of such esters with zinc. Careful analysis shows that the first of the above formulas probably represents the principal constituent. 1

(b) PREPARATION OF THE METALLIC SALT First method The acid ester resultingi'rom step (a) above was mixed with enough water to make a 15-20% mixture. This solution was made neutral to phenolphthalein with aqueous caustic. The acid was neutralized at 80-90 C. To the sodasalt solution was added an aqueous solution of zinc chloride. The reaction mixture was stirred at 80-90 C. for fifteen minutes, and then allowed to settle. The time required for the separation of the water from the salt was about fifteen minutes. and the zinc salt dissolved in twice its volume of benzene. The water and benzene were removed by vacuum distillation at about seven inches vacuum. The maximum temperature of distillation was 100 C. A typical batch in the preparation of the zinc salt of the reaction product of phosphorus 'pentasulphide and methyl cyclohexanol was as follows:

Grams of salt obtained 980 Per cent yield 89.5 Time of reaction between NaOH and acid 15 minutes Time of reaction between Na salt and ZnClz 15 minu Temperature of reaction, C.: Na0H+acid 80-90 Na salt-i-ZnClz 80-90 C. c. of benzol used for dehydration 2000 Temperature of dehydration- 100 C. maximum Pressure of dehydration--- 23" of Hg Second method Grams Methyl cyclohexanol a. 865 Phosphorus pentasulphide 333 Zinc oxide The water was then poured oi! The phosphorus pentasulphide is added over a period oi about 40 minutes so that the temperature does not exceed 212 F. The temperature is then raised to 320 F. over a period of one hour and maintained at that temperature for an additional one-halt hour. The yield of product is 1167 grams, and may be:

(a) Dissolved in an equal weight of mineral ofl and filtered hot after the addition of 2% by weight of a filter aid such as Filtrol; or

(b) Dissolved in an equal weight or benzol, filtered, and the benzol removed by evaporation under vacuum.

Third method The materials and the amounts are the same in this method as in the second method. The methyl cyclohexanol and phosphorus pentasulphide are mixed in a flask and maintained at a temperature of 212 F. by means of a water bath for seven hours. The zinc oxide is then added, and the temperature raised over a period 01' one hour to 320 F., and maintained at that temperature for one hour. The yield is 1170 grams, and the final solution and purification may be the same as for the second method.

Fourth method Pounds Methyl cyclohexanol 2975 Phosphorus pentasulphide 1137.5 Zinc oxide 391 The methyl cyclohexanol and phosphorus pentasulphide are heated to 210 F., and the temperature is maintained there for five and one-half hours. The pressure is then reduced to give a vacuum equivalent to five inches of mercury, absolute pressure, for one-half hour to remove the unreacted alcohol, hydrogen sulphide, etc. The mixture is cooled to 140 F. and zinc oxide added.

The temperature is maintained at 140 F. for

three hours. A vacuum equivalent to three inches of mercury, absolute pressure, is applied and the temperature raised to 210 F., and that temperature maintained for nine hours. Three thousand pounds of a neutral oil are added together with 2% of filter aid, and the solution is filtered at a temperature 01 about 200 F. The yield of product, exclusive of the oil, is 3800 pounds.

Generally, these reaction products are prepared by mixing the reactants and exposing the mixture to reaction conditions which produce the primary reaction product without any substantiail decomposition of such primary reaction produc The sulphur reactivity test is run as follows:

1.5 grams oi the compound are weighed to the nearest .1 milligram into a glass-stoppered, widemouthed Erlenmeyer fiask equipped with a refiux condenser and a stirring device. ml. of solvent and two 1" square pieces 01' 40 mesh copper gauze 1 are then added. The solution is maintained at the desired temperature by placing the flask in a constant temperature bath; or, it preferred, the temperature may be controlled by se lecting a solvent having a boiling point at the The copper is cleaned, before usin b be tin t 100 7 cherry red and immersing in methyl sl ohoi g o a desired temperature and heating the flask until refluxing takes place. The solution is refluxed for two hours and a third piece of copper gauze is added and the refluxing continued for 30 minutes. This process is repeated until the last piece of gauze added remains bright for the entire 30 minute reflux period.

The solvent is removed by decantation and the flask and gauze are washed with acetone and dried. During the washing, care must be taken to prevent loss of CuS which flakes off the gauze pieces. The washed and dried flask containing the reacted copper gauze is transferred to an air-tight system and H28 is liberated by treating the gauze with HCl. The evolved HzS is absorbed in CdClz solution. When no more H2S is evolved, the system is swept with nitrogen. The CdClz is then made just acid to litmus with HCl and titrated with standard iodine solution using starch as an indicator.

The solvents used, together with the results of the active sulfur tests are shown on the following table.

1 Solutions not refluxed. 1 Compound decomposed completely, forming tars which coated Cu gauze and prevented proper reaction.

One of the particular uses of the materials comprising the present invention is in lubricating compositions, and for specific data as to the effect of the same in lubricating compositions, reference may be had to the specification of my parent application which is now Patent No. 2,261,047, dated October 28, 1941.

In addition to their utility in lubricating compositions, the materials of this invention will be found useful as corrosion inhibitors in the protection of metalsurfaces generally-for example, in paint compositions; in cleaning compositions; and in solvents generally. 1

It will be noted that the new materials of this invention contain, in a single compound, the combination of an alkylated cycloaliphatic radicle, a thiophosphate radicle, and a polyvalent metal. It has been discovered that this combination of constituents produces a material having a particularly desirable combination of properties for use in lubricating oil to be used in the crankcases of internal combustion engines under conditions of severe service. This combination of properties includes the following:

In the past, it has not been found possible to compound addition agents which would reduce corrosive tendencies, and the tendency to produce acidic materials during oxidation, without increasing the tendency to form deleterious deposits. By the use of the addition agents of this invention, however, the corrosive tendency and the formation of acidic materials are reduced while, at the same time, reducing the tendency to form harmful deposits.

Another example of my new composition is the cobaltous salt of the acidic reaction product of P235 and hydrogenated amyl phenol, or as otherwise known, amyl cyclohexanol. Such material may be conveniently produced in accordance with the following:

800 grams of amyl cyclohexanol and 211 grams of Passv are mixed in 1000 cc. of benzene, and the mixture refluxed for about 4 hours. The resultant product in benzene solution is washed with warm water, four times in the instant case. The benzene was removed by distillation under vacuum leaving a residue of 920 grams of product.

200 grams of the foregoing acidic reaction product were neutralized with aqueous sodium hydroxide solution at a temperature of C., using an equivalent amount of sodium hydroxide. To the neutralized mixture was added an equivalent amount of cobaltous chloride (COClz). The resultant oil layer product comprising the cobaltous salt was dissolved in benzene and washed with water. Water and benzene were then removed by ordinary distillation methods, preferably under vacuum.

209 grams of the cobalt derivative were obtained analyzing 9.5% sulphur, 5.3% phosphorus, and 13.7% cobalt. The product was oil-soluble at 1% concentration in a refined mineral oil.

The foregoing example is typical of production of metallic salts by double decomposition from the sodium salt of the acid.

Another polyvalent metallic salt is the barium salt of the acidic reaction product of P285 with tertiary butyl cyclohexanol. Such salt may be conveniently produced in accordance with the following:

5 moles'of tertiary butyl cyclohexanol and 1 mole of P235 are heated together for 4 hours at C. A solid product is obtained which is dissolved in benzene, washed, and the solvent removed.

438 grams of this acid, 100 grams of methyl cyclohexanol, 100 cc. of methanol, .74 grams of barium oxide (5% excess by weight BaO) are heated together for a period of 1 hour at 60 C. At the end of this period, the temperature is increased to 100 C. and maintained there for an additional 1 hour. Following this, the pressure on the system is reduced to 5" Hg absolute pressure to remove solvents.

The resultant product was dissolved in a light mineral oil (about SAE 10) and filtered using Hyflo. The filtrate was the product and was obtained in a yield of 86%, or 860 grams.

' This product was oil-soluble and analyzed 5.85% sulphur, 2.84% phosphorus and 5.95% barium.

The following table gives additional examples of polyvalent metal salts of the acidic reaction product of P235 and methyl cyclohexanol. In the column headed Additional alcohol percent based on final composition, the indicated percent of alcohol was added for purposes of aiding solution in mineral oil. The analyses are results obtained upon analysis of the final composition.

TABLE I Mole ratio source of P01 Method Additional alcohol per Analysis of m mmpo'mon Mineral Metal oglloogol valem Mam Used I :83: lam?! on final on I e r um! Per cent Per cent Per cm Per cent 5:1 dd none 10. 6 7. 7 3. 2 6:1 dn 7.3% methyl cyclohexyl. 6. 8 3.0 6. 50 l dn methyl cyclohexyL- 7. 3 3. 8 7. 2 50 5: 1 dn 12% methyl cyclohexyL- 6. 2 2. 9 1. 6 62 5:1 dd 11. 5 7. 0 5:1 dd 7. 4 3. 8 3. l 50 5:1 (in 7. 7 3. 9 3.3 50 it it 2;; 3'2 5'3 60 Magnesium 5:1 dd 7.9 3. 1

gan 5:1 MnO;.. dn 8.2 4.0 1.6 60 Nickel 5: l Ni(NO|)r-6H2O- dd .--d0 7. 6 3. 7 3. 3 50 t bers" a: ea 3% a: a: a

1n t 2. I1 gtrontiumgr( Q H);-8H;O.. gar l0%emethyl cyclohexyL- 1g: 13 l 50 mo n a non Zinc 5: 1 21100; dd 11. 3 8. 0 9. 4 Zinc 5: l Z110 dn ---d0 7. 8 4. 0 3. 9 50 1 dd indicates "double decomposition" from sodium, or alkali metal salt; dn indicates direct neutralization" The terms alky and "alkylated as used herein are intended to include substituents, and substitution of substituents, of the cyclo-alkyl type as well as the straight chain type.

The terms propyl, butyl, and amyl as used herein are intended as inclusive terms defining all of the alkyl groups with the indicated number of carbon atoms (that is, 3, 4, and 5 carbon atoms respectively). For example, propyl is intended to be inclusive of propyl and iso-propyl; butyl of normal butyl, secondary butyl, iso-butyl, and tertiary-butyl; and amyl of normal, secondary normal, primary iso, secondary iso, the tertiary-amyl, and the di-ethyl-methyl groups.

The compositions of matter of this invention include the compounds derived from alkylated cycloaliphatic alcohols which include substituents in addition to the alkyl groups. Organic radicles in the ultimate composition may contain both alkyl groups and other subs'tituents attached to the cycloaliphatic nucleus. There may be also a plurality of alkyl groups of the same or difierent identity and a plurality of other substituents of the same or difierent identity attached to the same or difierent cycloaliphatic nuclei.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of 'the following claims or the equivalent of such be employed.

I therefore particularly point out and distinctly claim as my invention:

1. As a new composition of matter, the zinc salt of di(methylcyclohexyl) dithiophosphate.

2. As a new composition of matter, the product obtained by reacting together zinc oxide, phosphorus pentasulphide, and an alkylated cycloaliphatic alcohol.

3. As a new composition of matter, the product obtained by reacting together zinc oxide, phosphorus pentasulphide, and an alkylated cycloaliphatic alcohol in which substantially all of the alkyl groups have less than six carbon atoms.

4. As a new composition of matter, the product obtained by reacting together zinc oxide, phosphorus pentasulphide, and an alkylated cycloaliphatic alcohol having the hydroxyl group ditzectly attached to a. cycloaliphatic ring carbon a m.

5. As a new composition of matter, the product obtained by reacting together zinc oxide, phosphorus pentasulphide, and an alkylated cyclohexanol.

6. As a new composition of matter, the product obtained by reactin together zinc oxide, phosphorus pentasulphide, and methyl cyclohexanol.

7. The method of producing a salt-ester of a thiophosphoric acid which comprises reacting a polyvalent metal compound of the class consisting of the oxides, carbonates, basic carbonates, and hydroxides, with the reaction product of phosphorus pentasulphide and an alkylated cycloaliphatic alcohol in which substantially all of the alkyl groups have less than six carbon atoms.

8. As a composition of matter, a salt ester of a thiophosphoric acid produced by the method which comprises reacting a. polyvalent metal compound of the class consisting of oxides, carbonates, basic carbonates, and hydroxides with the reaction product of phosphorus pentasulphide and an alkylated cycloaliphatlc alcohol in which substantially all of the alkyl groups have less than six carbon atoms.

9. As a composition of matter, a salt ester of a thiophosphoric acid produced by the method which comprises reacting a basic polyvalent metal compound of the class consisting of oxides, carbonates, .basic carbonates, and hydroxides with the reaction product of phosphorus pentasulphide and an alkylated cycloaliphatic alcohol in which substantially all of the alkyl groups have less than six carbon atoms.

-. PETER A. ASSEFF.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,261,047 Asseff Oct. 28, 1941 2,364,283 Freuler Dec. 5. 1944 2,369,632 Cook et al Nov. 13, 1945 

8. AS A COMPOSITION OF MATTER, AS SALT ESTER OF A THIOPHOSPHORIC ACID PRODUCED BY THE METHOD WHICH COMPRISES REACTING A POLYVALENT METAL COMPOUND OF THE CLASS CONSISTING OF OXIDES, CARBONATES, BASIC CARBONATES, AND HYDROXIDES WITH THE REACTION PRODUCT OF PHOSPHORUS PENTASULPHIDE AND AN ALKYLATED CYCLOALIPHATIC ALCOHOL IN WHICH SUBSTANTIALLY ALL OF THE ALKYL GROUPS HAVE LESS THAN SIX CARBON ATOMS. 